EP2251313A1 - Matériau piézoélectrique du type sans plomb - Google Patents

Matériau piézoélectrique du type sans plomb Download PDF

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EP2251313A1
EP2251313A1 EP09718943A EP09718943A EP2251313A1 EP 2251313 A1 EP2251313 A1 EP 2251313A1 EP 09718943 A EP09718943 A EP 09718943A EP 09718943 A EP09718943 A EP 09718943A EP 2251313 A1 EP2251313 A1 EP 2251313A1
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piezoelectric
lead
pzt
materials
piezoelectric material
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EP2251313B1 (fr
EP2251313A4 (fr
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Xiaobing Ren
Wenfeng Liu
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National Institute for Materials Science
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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    • C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
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    • C04B35/62605—Treating the starting powders individually or as mixtures
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Definitions

  • the present invention relates to a lead-free piezoelectric material containing no toxic element such as Pb.
  • Piezoelectric materials have an effect of expanding and contracting when a voltage is applied (electrostrain effect) and reversely generating a voltage when pressure is applied (piezoelectric effect). Therefore they are a very important group of substances which can convert mechanical energy to electric energy. These materials have been widely applied to products in the field of energy conversion, such as actuators and sensors, and are widespread from daily life to cutting-edge technologies, playing an essential role in today's society.
  • PZT Pb(Ti,Zr)O 3 polycrystal
  • additive-free PZT has a maximum piezoelectric coefficient d 33 of about 220 pC/N
  • soft PZT improved by addition has a maximum piezoelectric coefficient d 33 of about 400 to 580 cp/N. Therefore they have been synonymous with piezoelectric materials in the past half century.
  • PZT contains a large amount of toxic lead, strict regulations have now been imposed on them from environmental reasons. Accordingly, developing a high performance lead-free piezoelectric material comparable to PZT is an urgent problem in the world.
  • KNN-LT and KNN-LN based materials have serious flaws of the difficulty in synthesis and high cost due to a large amount of expensive elements of Ta, La in the materials.
  • Non-Patent Document 1 Zhi Yu, Ruyan Guo, and A. S. Bhalla, Dielectric behavior of Ba(Ti1-xZrx)O3 single crystals. J. Appl. Phys. 88, 410 (2000 )
  • Non-Patent Document 2 T. Mitsui and W. B. Westphal, Dielectric and X-Ray Studies of CaxBa1-xTiO3 and CaxSr1-xTiO3. Phys. Rev. 124, 1354-1359 (1961 )
  • an object of the present invention is to provide a lead-free piezoelectric material capable of showing a high piezoelectric coefficient (d 33 > 500 pC/N) exceeding that of soft PZT.
  • Invention 1 is a lead-free piezoelectric material containing no toxic element such as Pb, comprising a pseudo-binary solid solution of ⁇ [(Ba 1-x1 M1 x1 ) ((Ti 1-x Zr x ) 1-y1 N1 y1 )O 3 ]- ⁇ % (Ba 1-y Ca y ) 1-x2 M2 x2 ) (Ti 1-y2 N2 y2 ) O 3 ] ⁇ (wherein M1, N1, M2 and N2 represent an additive element)(abbreviated as BZT- ⁇ %BCT).
  • Invention 2 is the lead-free piezoelectric material according to Invention 1, wherein the pseudo-binary solid solution has a morphotrophic phase boundary (MPB).
  • MPB morphotrophic phase boundary
  • BZT-8%BCT has a morphotrophic phase boundary (MPB) ( Figure 1 illustrating an example of [Ba(Ti 0.8 Zr 0.2 )O 3 ]- ⁇ %[(Ba 0.7 Ca 0.3 )TiO 3 ]), and a piezoelectric material has extremely high piezoelectric properties (d 33 > 580 pC/N) exceeding that of PZT at a composition near the MPB ( Figures 2 and 3 ).
  • a material using a pseudo-binary solid solution which has a MPB is invented based on the above findings.
  • the piezoelectric coefficient of the inventive material is higher than that of conventional soft PZT (d 33 > 400 pC/N) and is comparable to that of PZT-5H, the number-one soft PZT ( Figure 3 ).
  • KNN materials are composed of extremely stable oxide, they have no problem of volatility as in KNN materials or (Bi 0.5 Na 0.5 )TiO 3 . They have excellent sintering properties and thus can be produced very easily. Also, since no expensive raw material such as Nb or Ta is used, raw material and manufacturing costs are low. Moreover, there is no problem of deliquescence or sensitivity to moisture like KNN materials.
  • the material proposed in the present invention is a potential alternative to PZT in the applications at about room temperature or lower.
  • Two terminal compositions used in the present invention include Ba(Ti 1-x Zr x )O 3 having a rhombohedral (R) structure and (Ba 1-y Ca y )TiO 3 having a tetragonal (T) structure.
  • R rhombohedral
  • Ba 1-y Ca y tetragonal
  • x 0.1 to 0.5.
  • Figure 1 shows a phase diagram of a pseudo-binary solid solution [Ba(Ti 0.8 Zr 0.2 )O 3 ]- ⁇ %[(Ba 0.7 Ca 0.3 )TiO 3 ] as an example of a phase diagram of a pseudo-binary solid solution composed of the above two terminal compositions.
  • the present invention also includes pseudo-binary lead-free piezoelectric materials shown in the following Examples, in which some of the elements are substituted with an element of the same valence as constituent ions.
  • the materials are represented by ⁇ [(Ba 1-x1 M1 x1 ) ((Ti 1-x Zr x ) 1-y1 N1 y1 )O 3 ]- ⁇ % [(Ba 1-y Ca y ) 1-x2 M2 x2 ) (Ti 1-y2 N2 y2 )O 31 ] ⁇ (wherein M1,N1,M2 and N2 represent an additive element).
  • BZT-BCT has an A 2+ B 4+ O 3 perovskite structure, Ba 2+ and Ca 2+ occupy the A 2+ site, and Ti 4+ and Zr 4+ occupy the B 4+ site.
  • the "element of the same valence as constituent ions” means an element having a valence of 2+ (e.g., Sr 2+ ) when substituting in the A 2+ site, and an element having a valence of 4+ (e.g., Hf 4+ , Sn 4+ ) when substituting in the B 4+ site.
  • an "additive element of the same valence” may be prepared by combining elements having a different valence (for example, elements may be substituted with 1/2Bi 3+ 1/2Na + (average valence being 2+) in the A 2+ site).
  • addition of an acceptor additive element is a common improvement method for reducing the loss of piezoelectric materials.
  • a material prepared by using BZT-BCT and improved by the “addition of an acceptor additive element” is also included in the scope of the present invention.
  • some of the elements may be substituted with a "donor additive element".
  • the "addition of a donor additive element” is a common improvement method for increasing piezoelectric properties of piezoelectric materials.
  • a material prepared by using BZT-BCT and improved by the “addition of a donor additive element” is also included in the scope of the present invention.
  • Some of the elements may be simultaneously substituted with both of an "acceptor additive element” and a “donor additive element”.
  • Figure 1 is a phase diagram of a pseudo-binary solid solution [Ba (Ti 0.8 Zr 0.2 )O 3 ]- ⁇ %[(Ba 0.7 Ca 0.3 )TiO 3 ].
  • Raw materials BaZrO 3 (99.9%), CaCO 3 (99.9%), BaCO 3 (99. 9%) and TiO 2 (99.9%)
  • Standardized solid phase sintering process Synthesized at 1350°C for 2 hours and sintered at 1450°C for 3 hours. (The temperature needs to be 1200°C to 1400°C for the synthesis and 1300°C to 1500°C for sintering.)
  • Polarization conditions An electric field of about twice the coercive field is applied to a sample at the Curie temperature (110°C) or higher and the sample is gradually cooled to room temperature.
  • the samples are a disk having a thickness of 6.5 mm and a diameter of 8 mm.
  • the piezoelectric coefficient d 33 is measured by a Model ZJ-6B d 33 meter.
  • the electric field-displacement was measured by Workstation and MTI2000 Photonic Sensor made by Radiant Technologies Inc.
  • Figure 2 is based on the measured values (Table 1) of the relationship between the piezoelectric coefficient d 33 and the composition ⁇ % at room temperature.
  • Figure 2 shows that the material has a high piezoelectric coefficient near the MPB.
  • the present invention provides a lead-free piezoelectric material using the MPB.
  • [Table 1] Ba(Zr 0.2 Ti 0.8 )O 3 - ⁇ %(Ba 0.7 Ca 0.3 )TiO 3 ⁇ d 33 (pC/N) 10 10 20 20 30 30 40 230 45 356 50 584 55 236 60 212 70 165 80 52 90 40
  • the lead-free piezoelectric material of the present invention has piezoelectric properties twice or several times higher than that of other lead-free piezoelectric materials, but also the piezoelectric properties exceed those of most PZT materials.
  • the figure demonstrates the innovativeness of the present invention.
  • Non-lead family d 33 (pC/N)(typical value) Ba(Zr 0.2 Ti 0.8 )O 3 -50%(Ba 0.7 Ca 0.3 )TiO 3 584 bismuth layer structured 50 tungsten bronze structured 50 (BiNa)TiO 3 based 125 BaTiO 3 based 148 KNbO 3 based 230 PZT family Pb(Zr 0.52 Ti 0.48 )O 3 220 PZT-8 220 PZT-4 289 PZT-5 400 PZT-5H 590
  • the piezoelectric material of the present invention can be used in almost all of the applications of conventional PZT and other piezoelectric materials at about room temperature (up to 70°C). Some examples are shown below.
  • Electronic sound sources for home electric appliances and clocks Underwater exploration sources for fishfinders and sonars Ignition sources for gas lighters Exploration sources for solid such as metal, concrete and earth crust Atomization sources for humidifiers and inhalers Ultrasonic sources for various cleaners Back sonars and corner sensors for automobiles Pumps for inkjet printers Inverter transformers for liquid crystal monitors Microactuators for scanning electron microscopes Ultrasonic sources for medical diagnostic devices and massaging tools Clock signal sources for phones and remote controllers Counters for pedometers Touch sensors for PC monitors

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EP09718943.5A 2008-03-11 2009-03-10 Matériau piézoélectrique du type sans plomb Not-in-force EP2251313B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008061044A JP5344456B2 (ja) 2008-03-11 2008-03-11 非鉛系圧電材料
PCT/JP2009/054540 WO2009113535A1 (fr) 2008-03-11 2009-03-10 Matériau piézoélectrique du type sans plomb

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EP2251313A1 true EP2251313A1 (fr) 2010-11-17
EP2251313A4 EP2251313A4 (fr) 2012-11-21
EP2251313B1 EP2251313B1 (fr) 2014-07-30

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US (1) US8182713B2 (fr)
EP (1) EP2251313B1 (fr)
JP (1) JP5344456B2 (fr)
KR (1) KR101251745B1 (fr)
CN (1) CN101970374B (fr)
WO (1) WO2009113535A1 (fr)

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EP2584622A3 (fr) * 2011-10-20 2014-12-31 Canon Kabushiki Kaisha Dispositif piézoélectrique, dispositif d'extraction de poussière et appareil d'imagerie
EP2866272A1 (fr) * 2013-10-25 2015-04-29 Seiko Epson Corporation Élément piézoélectrique, tête d'éjection de liquide, appareil d'éjection de liquide, actionneur, capteur et moteur
US20150349239A1 (en) * 2014-05-30 2015-12-03 Canon Kabushiki Kaisha Piezoelectric material, piezoelectric element, and electronic device
EP3053174A1 (fr) * 2013-10-02 2016-08-10 Epcos AG Condensateur céramique multicouche à base de bati(1-y)zryo3
US9981292B2 (en) 2014-05-30 2018-05-29 Canon Kabushiki Kaisha Piezoelectric material, piezoelectric element, method for manufacturing piezoelectric element, and electronic device

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JP2011181764A (ja) * 2010-03-02 2011-09-15 Tdk Corp 圧電体素子及びその製造方法
JP2011243722A (ja) * 2010-05-18 2011-12-01 Seiko Epson Corp 圧電素子、液滴噴射ヘッドおよび液滴噴射装置
CN101935212A (zh) * 2010-09-09 2011-01-05 西北工业大学 一种锆钛酸钡钙无铅压电陶瓷及其制备方法
JP5979992B2 (ja) 2011-07-05 2016-08-31 キヤノン株式会社 圧電材料
EP2729971B1 (fr) 2011-07-05 2017-06-07 Canon Kabushiki Kaisha Matériau piézoélectrique
CN102503409A (zh) * 2011-11-02 2012-06-20 聊城大学 一种锡钛酸钡钙无铅压电陶瓷及其制备工艺
CN104302598A (zh) * 2012-03-16 2015-01-21 佳能株式会社 压电材料、压电元件和电子装置
US9660175B2 (en) 2012-03-30 2017-05-23 Canon Kabushiki Kaisha Piezoelectric ceramic, method for manufacturing piezoelectric ceramic, piezoelectric element, and electronic device
CN104205388B (zh) 2012-03-30 2017-03-15 佳能株式会社 压电陶瓷、压电元件、液体喷射头、超声马达和除尘装置
CN102815938B (zh) * 2012-08-27 2014-08-06 天津大学 一种钛酸钡基无铅电致伸缩陶瓷及其制备方法
TWI581472B (zh) 2012-11-02 2017-05-01 佳能股份有限公司 壓電材料、壓電元件、及電子裝置
TWI545814B (zh) 2012-11-02 2016-08-11 佳能股份有限公司 壓電式材料、壓電式元件及電子設備
EP2749550B1 (fr) 2012-12-28 2017-05-17 Canon Kabushiki Kaisha Matériau piézoélectrique, élément piézoélectrique et appareil électronique
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US8182713B2 (en) 2012-05-22
EP2251313B1 (fr) 2014-07-30
CN101970374B (zh) 2013-11-06
WO2009113535A1 (fr) 2009-09-17
US20110037015A1 (en) 2011-02-17
JP2009215111A (ja) 2009-09-24
KR101251745B1 (ko) 2013-04-05
EP2251313A4 (fr) 2012-11-21
JP5344456B2 (ja) 2013-11-20
CN101970374A (zh) 2011-02-09
KR20110016864A (ko) 2011-02-18

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